Syntheses,Structures and Properties of Two New Coordination Polymers with Flexible Ligands as Linkers

Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1^2- anions connecting the Zn2（O2C）4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2^- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional（3D） supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.

Two Cadmium(II) Coordination Polymers from Flexible Bis(imidazolyl) Ligands

The hydrothermal reaction of 1,4-bis（imidazol-1-yl）butane （bimb） and 1,4-bis（2- methylimidazol-1＇-yl）butane （bmib） with CdBr2·4H2O gave rise to two coordination polymers, [Cd（bimb）2Br2]n （1） and [Cd（bmib）Br2]n （2）, respectively. Single-crystal X-ray diffraction analysis reveals that 1 and 2 crystallize in the monoclinic space group P21/n and the orthorhombic space group Pccn, respectively. In 1, bimb adopts an anti-anti-anti conformation and bridges adjacent Cd（Ⅱ） to form a two-dimensional （2D） network containing rhombohedral rings. The 2D layers are arranged in an offset ABCABC sequence to fill large void in the rhombohedral rings. In 2, bmib also exhibits an anti-anti-anti conformation, but it links neighboring Cd（Ⅱ） into a one-dimensional （1 D） chain. Br in 1 and 2 serves as a monodentate ligand to balance charge.

The Effects of Metal Ions and Secondary Ligands on the Formation of Structures Resulted from Flexible Building Blocks

Two coordination polymers have been synthesized from cpg/4,4＇-bipy/metal ions reaction system, [Zn（cpg）（4,4＇-bipy）0.5（H2O）]·H2O 1 and [Cd（cpg）（4,4＇-bipy）0.5（H2O）2]·H2O 2. X- ray analyses show that different coordination geometries of zinc and cadmium ions lead to similar ladder structures （tetra-for zinc ion and hexa- for cadmium ion）, in which all the flexible cpg molecules exist as single conformations of anti-form.

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

Three new supramolecular polymers, [（IP）（H2SO4）（H2O）]（1）, [（H2SDC）（BPA）]（2） and [Mn（SDC）（IP）2]n （3）, have been constructed by three modes（rigid IP, rigid SDC ＋ flexible BPA, rigid IP ＋ rigid SDC）. Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.

A Mn(Ⅱ) Coordination Polymer with the Flexible Tripodal Ligand 1,3,5-Tris-(imidazol-1-ylmethyl)benzene

A new Mn（Ⅱ） coordination polymer {[Mn（timb）2（H2O）2]·（Cl）2·（H2O）2}n（1,timb = 1,3,5-tris-（imidazol-1-ylmethyl）benzene） has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774（13）,b=9.8720（15）,c=11.4898（16）A,α=93.378（3）,β= 95.471（3）,γ=101.101（3）°,V=1002.6（3）A^3,Mr=834.67,Dc=1.382 g/cm^3,μ（MoKα）=0.517mm^-1,F（000）=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I〉2σ（I）.It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.

Two Interpenetrated Dia-type Coordination Polymers Constructed from Mixed Dicarboxylate and Bis(imidazol)-based Ligands

Two novel interpenetrating diamond frameworks, namely [Cd（mal）（bix）]n （1）and {[Zn（sub）（bib）]n.H2O}. （2）（H2mal = maleic acid, H2sub = suberic acid, bix = 1,4-bis（imidazol- l-ylmethyl）-benzene, bib = 1,4-bis（N-imidazolyl）butane） were hydrothermally synthesized and characterized by elemental analysis, infrared spectra （IR）, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the orthorhombic system with space group Pnma and features a 3-fold interpenetrating diamond framework. Compound 2 exhibits a 4-fold interpenetrating diamond network. The luminescent properties of these two compounds have also been investigated in detail.

Topology and Photoluminescence Property of a Neodymium-carboxylate Coordination Polymer Based on a Tripodal Flexible Ligand

A new metal-organic coordination polymer {[Nd（tci）（H2O）2]·2H2O}n（1） has been synthesized based on the flexible tricarboxylate ligand tris（2-carboxyethyl）isocyanuric acid（H3tci） and structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, infrared spectra（IR）, powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）. Complex 1 crystallizes in triclinic, space group P1 with a = 9.1648（11）, b = 9.3326（12）, c = 12.440（2） , C（12）H（20）N3O（13） Nd, Mr = 558.55, V = 886.9（2） 3, Z = 2, Dc = 2.092 g·cm-3, μ = 3.006 mm-1, F（000） = 554, 2.56〈θ〈25.00°, λ（Mo Kα） = 0.71073 , T = 293（2） K, the final R = 0.0662 and w R = 0.2071. X-ray diffraction analysis reveals that complex 1 is a two-dimensional layer, which is further assembled into a three-dimensional supramolecular architecture through hydrogen bonding interactions. The structure of complex 1 can be simplified as a rare 2-periodic uninodal {48·62} topology and a non-interpenetrating kgd topology. Furthermore, the thermal stability and photoluminescence property of 1 were investigated.

Syntheses,Crystal Structures and Properties of Two New Compounds from a Flexible Bipodal Acid with Additional Amide Groups

Two novel compounds {[Cu（IBG）（4,4-bipy）（H2O）2]2·11H2O}n（1） and {[Co（IBG）-（μ-H2O）（H2O）2]·2H2O}n（2） based on isophthaloylbisglycine（H2IBG） have been synthesized and structurally characterized by thermogravimetric analysis, elemental analysis and single-crystal X-ray diffraction. Compound 1 shows a 1D chain sine/cosine chain structure, and compound 2 can be characterized as a 4-connected sql tetragonal planar network with the point symbol of {44·62}. Compound 2 has been characterized by magnetic measurements. In addition, 1 and 2 display an interesting reversible crystal-to-amorphous transformation.

Syntheses and Crystal Structures of Three Cadmium（II） Coordination Complexes Based on Flexible 1,2-Bis（imidazol-1~ˊ-yl）ethane

Three Cd（II） coordination complexes,{[Cd（bime）3]（NO3）2·（H2O）3}n（1）,[Cd（bime）Br2]n（2） and [（H2bime）（CdBr4）（H2O）]n（3）（bime = 1,2-bis（imidazol-1-yl）ethane）,have been prepared and characterized.Single-crystal X-ray diffraction analysis reveals that 1~3 crystallize in the trigonal space group P-3,monoclinic space group C2/c and triclinic space group P1,respectively.In 1,bime bridges six-coordinated Cd（II） to generate a two-fold interpenetrating 3D coordination polymer,in which NO3- is not involved in coordination,but serves as a void filler to balance the charge of the 3D framework.The six NO3- and six uncoordinated water molecules form an unprecedented 24-membered macrocycle through hydrogen bonding interaction.In 2,bime in an anti-conformation links the CdBr2 units into a zigzag chain.In 3,bime does not take part in coordination,but is protonated to act as a counter cation of [CdBr4 ]2-.The hydrogen bonds between H2bime and [CdBr4]2- result in the formation of a supramolecular chain.

Anion Directed Assembly of Cu(Ⅱ)Complexes Formed by a Flexible Ligand

Coordination polymers,consisting of metal,anion and organic ligands,have attracted much attention.The structure of coordination polymers is affected by various factors.To investigate the effects of anion,syntheses and structures of four Cu(II)complexes,namely[(Cu LCl)(PF)](1),[(Cu LCl)(ClO)](2),[(Cu LCl)?CHOH](3)and Cu LCl(4),are reported based on a flexible ligand,1,3-bis(2-pyridylmethyl)imidazolium(L).The ligand is accommodative to kinds of anions,and forms 1-D chains generally upon reaction with Cu(II)salts.The effect is measured by the conformational variation through the dihedral angles between different aromatic rings of the ligand.In order to further investigate the effect of anion,a protonated sample of L,namely,LH(ClO)?HO(5)is also synthesized and structurally characterized,showing an intriguing hydrogen bonded helix.

Syntheses and Crystal Structures of Two One-dimensional Cobalt(Ⅱ) Compounds with the Flexible Dipyridyl Ligand

Two one-dimensional cobalt（II） compounds {[Co（Hbpma）（H20）4]2·3SO4·4.5H2O}n 1 and {[Co（Hbpma）（NCS）3（H20）]·2.85H2O}n 2 （bpma = N,N＇-bis（3-pyridylmethyl）amine） have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group Pi with a = 15.8780（5）, b = 16.2187（5）, c = 16.4858（5） A, α = 91.0420（10）,β = 94.5190（10）, γ = 101.4360（10）°, V = 4145.7（2） A3, C24H53Co2N6024.5083, Mr = 1031.76, Z = 4, Dc = 1.653 g/cm3, p（MoKa） = 1.046 mm-1, F（000） = 2148, S = 1.017, the final R = 0.0269 and wR = 0.0644 for 13032 observed reflections （I 〉 2a（/））. For complex 2, it belongs to triclinic, space group Pi with a = 9.3761（11）, b = 10.5814（13）, c = 11.2972（14）A, α= 85.472（2）,β = 88.058（2）,γ = 76.203（2）°, V= 1085.0（2） A3, C15Hzl.v0CoN603.85S3, Mr= 502.79, Z = 2, Dc = 1.539 g/cm3, p（MoKa） = 1.112 mm-1, F（000） = 519, S = 1.070, the final R = 0.0358 and wR = 0.0899 for 3466 observed reflections （I 〉 2σ（I））. Two complexes 1 and 2 are both found to be one-dimensional coordination polymers bridged by the protonated bpma ligands, which are assembled into three-dimensional supramolecular structures through the hydrogen bonding interactions and π-π packing interactions.

Synthesis and Crystal Structure of a New Coordination Polymer:{[AgL]ClO_4}_n (L=2,5-Bis(3-pyridinylmethylthio)-1,3,4-thiadiazole)

The title complex {[AgL]ClO4}n（L=2,5-bis（3-pyridinylmethylthio）-1,3,4-thiadiazole） was synthesized by the reaction of Ag（I） salt and a novel flexible ligand L.Its structure was determined by X-ray crystallography with the following data：monoclinic,space group P21/n,a=16.5068（13）,b=7.6548（4）,c=16.5521（13）A,β=115.119（3）o,V=1893.7（2）A^3,Z=4,Dc=1.893 g/cm^3,μ=1.565 mm^-1,F（000）=1072,C14H12AgClN4O4S3,Mr=539.78,T=293（2） K,S=1.067,the final R=0.0342 and wR=0.0870.The silver ion in the complex is in a trigonal coordination geometry to link three different L.Meanwhile,each L connects three different silver ions by its N coordination sites to form a two-dimensional layer structure.

Two Discrete Cu-Complexes Constructed from a Multidentate N-Containing Dinucleating Ligand

Two comparable discrete complexes [CuⅡ（CH3CN）2L2]·2（ClO4） 1 and [CuI2I2L2]·（DMF）2 2 were successfully synthesized by the reaction of CuⅡ and CuⅠ salts with a novel dinucleating ligand 2,5-bis（3-pyridinylmethylthio）-1,3,4-thiadiazole）（L）,respectively.Complex 1 presents a single nuclear structure while 2 has a dimeric structure where two CuI ions are doubly bridged by halide ions in a μ2-fashion.Both discrete molecules were outspreaded into a one-dimensional supramolecular chain via aromatic interactions such as C–H…π and π…π interactions.

Synthesis,Crystal Structure and Properties of a Novel Decavanadate Complex with One-dimensional Chain Involving Sodium and 'Bis-tris' Ligand

By using a flexible multidentate ligand,bis（2-hydroxyethyl）iminotris（hydroxyhydroxylmethy）methane（＇bis-tris＇：H5L）,the title complex {[Na（H6L）2]2}n·nV10O28（1） has been successfully synthesized under self-assembly condition and characterized by IR spectroscopy,elemental analysis,PXRD and single-crystal X-ray diffraction.The crystal structure belongs to an orthorhombic system,space group Cmca with a = 23.752（2）,b = 13.5360（8）,c = 18.5377（11） ,V = 5960.1（7）,Z = 8,Dc = 2.055 g/cm3,F（000） = 3744,μ = 1.630 mm-1,the final R = 0.0283 and wR = 0.0759 for 3353 observed reflections with I 〉 2σ（I）.This complex consists of decavanadate [V10O28]6-motifs as counter anions intercalated with one-dimensiond chains of the composition [Na（H6L）2]n3n＋.And significant intermolecular O-H…O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.

Zeolite-Encapsulated Fe（lll） Complex with 5,10,15,20-Tetraphenyl Porphyrin as Heterogeneous Catalysts for Epoxidation of α-Pinene： Synthesis, Characterization and Catalytic Activity

In this paper iron complex with 5,10,15,20-tetraphenyl porphyrin inside NaX zeolite nanocages was capsuled. All synthesized homogeneous and heterogeneous catalysts were applied for epoxidation of α-pinene. It has been shown that hydrophobic porphyrins are anchored inside the zeolite pores according to flexible ligand method. It also has been examined that capsulation of metalloporphyrins inside the pores of solid supports change catalytic activity and stability. All catalysts were characterized by Fourier transform infrared （FTIR）, UV/Vis diffuse reflectance spectroscopic （DRS）, scanning electron microscopy （SEM） analyses to confirm the complexes immobilization.

Syntheses and Crystal Structures of Two Cadmium(Ⅱ) Compounds Linked by N,N-Bis(3-pyridylmethyl)amine

Two cadmium（Ⅱ） compounds linked by a flexible dipyridyl ligand {[Cd2（Hbpma） Cl5（H2O）]·2H2O}n 1 and [Cd（Hbpma）Cl（H2O）2]2·2SO4·3H2O 2 （bpma = N,N-bis（3-pyridylmethyl）amine） have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P with a = 9.5612（6）, b = 11.3401（7）, c = 11.5069（12）, α = 112.8540（10）, β = 106.5330（10）, γ = 101.6680（10）°, V = 1030.77（14）3, C12H20Cd2Cl5N3O3, Mr = 656.36, Z = 2, Dc = 2.115 g/cm3, μ（MoKα） = 2.727 mm–1, F（000） = 636, S = 1.059, the final R = 0.0319 and wR = 0.0822 for 3443 observed reflections （I 2σ（I））. For complex 2, it belongs to triclinic, space group P with a = 10.9487（4）, b = 11.4197（4）, c = 15.4288（5）, α = 94.7470（10）, β = 104.1000（10）, γ = 104.42°, V = 1790.76（11）3, C24H42Cd2Cl2N6O15S2, Mr = 1014.46, Z = 2, Dc = 1.881 g/cm3, μ（MoKα） = 1.529 mm–1, F（000） = 1020, S = 1.050, the final R = 0.0178 and wR = 0.0451 for 6026 observed reflections （I 2σ（I））. Complex 1 is found to have tetranuclear Cd（Ⅱ） clusters which are bridged by the protonated bpma ligands leading to one-dimensional coordination polymers, whereas complex 2 consists of binuclear Cd（Ⅱ） structures linked by the protonated bpma ligands. Both complexes are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions.

A High Dimensional Coordination Polymer Based on [β-Mo_8_(O)_(26)]^(4-) Inorganic Building Block: Synthesis, Structure and Topology

A high dimensional copper coordination polymer {[Cu2（btb）2（H2O）4（ -Mo8O26）] H2O}n（1, btb = 1,4-bis（1,2,4-triazol-1-yl）butane） based on [ -Mo8O26]4 anions and flexible bis（triazole） ligands has been synthesized and characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction and thermal analysis. The crystallographic data show that complex 1 crystallizes in triclinic space group P with a = 9.7550（10）, b = 10.3996（11）, c = 10.9516（11）, = 77.622（2）, = 89.602（2）, = 87.610（2）, V = 1084.25（19）3, C16H34Cu2Mo8 N12O31, Mr = 1785.15, Dc = 2.734 g cm 3, μ（MoKα） = 3.303 mm 1, F（000） = 856, GOF = 1.060, Z = 1, the final R = 0.0376 and wR = 0.0982 for I 〉 2 （I）. In 1, the inorganic building block [ -Mo8O26]4 anions are connected with each other to generate one-dimensional chains. Then the chains are further connected by Cu2＋ ions to form a three-dimensional （3D） inorganic framework [Cu2（ -Mo8O26）]n containing quadrangular channels, with the pcu alpha-Po primitive cubic topology. The btb ligands are encapsulated into the void of the 3D inorganic framework forming a new three-dimensional architecture. The thermal analysis illustrates that complex 1 retains a comparatively good thermal stability.